Methods of applications for a mass spectrometer in combination with a gas chromatograph

ABSTRACT

Methods may include emplacing a wellbore tool in a wellbore, the wellbore tool including a gas chromatograph and a mass spectrometer, wherein the mass spectrometer is configured to operate at a pressure greater than 10−2 Torr, measuring a sample from the wellbore using the wellbore tool, and determining a molecular weight of one or more components of the sample from the measured response of the wellbore tool. Methods may also include establishing a library of one or more chemical components, emplacing a wellbore tool in a wellbore, the wellbore tool including a gas chromatograph and a mass spectrometer, wherein the mass spectrometer is configured to operate at a pressure greater than 10−2 Torr, measuring a sample from the wellbore using the wellbore tool, comparing the measured response from the wellbore tool for the sample with results from the library of one or more chemical components, and determining a molecular weight of one or more components of the sample.

BACKGROUND

As a wellbore is being prepared, samples of formation fluids may be obtained from downhole and analyzed onsite or sent to a full-scale laboratory. Analysis of the formation fluids may be beneficial for a variety of reasons including quantifying the quality and amount of the fluids and gasses entering the wellbore, assessing wellbore conditions for equipment installation downhole, and ensuring safe well site operation. The use of downhole measurement tools may be employed as operators seek to eliminate the need to obtain and transport samples of the formation fluids to the laboratory for further detailed analysis.

The analysis of wellbore fluids and gasses onsite may provide information about the maturity and nature of hydrocarbons in the accumulated source, compartmentalization of intervals in the reservoir being drilled, and oil quality, as well as information regarding production zones, lithology changes, history of reservoir accumulation, or seal effectiveness. However, downhole analysis using wellbore tools may be complicated by a number of factors. Wellbores may be small diameter holes having a diameter of approximately five inches or less when cased, which may constrain the geometry of the wellbore tool components. In addition, operating conditions for wellbore tools may be stringent, requiring designs that endure vibrations, elevated temperatures and high pressure environments.

SUMMARY

This summary is provided to introduce a selection of concepts that are described further below in the detailed description. This summary is not intended to identify key or essential features of the claimed subject matter, nor is it intended to be used as an aid in limiting the scope of the claimed subject matter.

In one aspect, embodiments of the present disclosure are directed to methods that include positioning a wellbore tool in a wellbore. The wellbore tool includes a gas chromatograph, a rotary valve configured to inject a fluid sample into the gas chromatograph, and a mass spectrometer. The mass spectrometer is configured to operate at a pressure greater than 10⁻² Torr and an inlet for the mass spectrometer receives an output from an outlet of the gas chromatograph. The mass spectrometer includes at least one of (a) an ion trap analyzer and (b) a quadrupole mass analyzer. The example methods further include measuring a sample from the wellbore using the wellbore tool, and determining a molecular weight of one or more components of the sample from the measured response of the wellbore tool. 1.

In another aspect, embodiments of the present disclosure may be directed to methods that include establishing a library of one or more chemical components and positioning a wellbore tool in a wellbore. The wellbore tool includes a gas chromatograph, a rotary valve configured to inject a sample into the chromatograph, and a mass spectrometer that is configured to operate at a pressure greater than 10-2 Torr and includes at least one of (a) an ion trap analyzer and (b) a quadrupole mass analyzer. The example methods include measuring a sample from the wellbore using the wellbore tool, comparing the measured response from the wellbore tool for the sample with results from the library of one or more chemical components, and determining a molecular weight of one or more components of the sample.

Other aspects and advantages of the disclosure will be apparent from the following description and the appended claims.

BRIEF DESCRIPTION OF FIGURES

FIG. 1 is a schematic depicting a wellbore tool in accordance with embodiments of the present disclosure.

FIG. 2 is a schematic depicting a wireline tool in accordance with embodiments of the present disclosure.

FIGS. 3 and 4 are flow diagrams indicating various tool configurations in accordance with embodiments of the present disclosure.

FIG. 5 is a schematic representations of combined gas chromatograph and mass spectrometers in accordance with embodiments of the present disclosure.

FIGS. 6.1 and 6.2 are schematic representations of a quadrupole mass analyzer in accordance with the present disclosure.

FIG. 7 is a schematic representation of a ion trap mass analyzer in accordance with embodiments of the present disclosure.

FIG. 8 is a schematic representation of a cylindrical ion trap mass analyzer in accordance with embodiments of the present disclosure.

FIG. 9 is a flow diagram indicating a mode of measuring the mass of a sample component by adjusting operating pressure in accordance with embodiments of the present disclosure.

FIG. 10 is a flow diagram indicating a mode of measuring the mass of a sample component by adjusting radio frequency (RF) in accordance with embodiments of the present disclosure.

FIG. 11 is a mass chromatogram of a non-biodegraded oil sample in accordance with embodiments of the present disclosure.

FIG. 12 is a mass chromatogram of a biodegraded oil sample in accordance with embodiments of the present disclosure.

FIG. 13 is a graphical representation of the total ion count for a sample in accordance with embodiments of the present disclosure.

FIGS. 14-15 are graphical representations of the specific ion measurement at 58 m/z for a sample in accordance with embodiments of the present disclosure.

FIG. 16 is a graphical representation of specific ion measurement at 58 m/z, 72 m/z, and 86 m/z for a sample in accordance with embodiments of the present disclosure.

FIG. 17 is a graphical representation of specific ion measurement at 58 m/z, 72 m/z, 86 m/z, and 100 m/z for a sample in accordance with embodiments of the present disclosure.

FIGS. 18-20 are mass spectra of three C7 components eluting at 786, 792, and 797 RF, respectively, for a sample in accordance with embodiments of the present disclosure.

DETAILED DESCRIPTION

This disclosure relates generally to methods and tools for analyzing formation fluid and gas compositions. More particularly, this disclosure relates to the determination of a formation fluid composition using a gas chromatograph and a mass spectrometer. Mass spectrometers in accordance with the present disclosure may be configured to operate at relatively high pressures, such as above 10⁻³ Torr. In one or more embodiments, instrument components in accordance with the present disclosure may have small overall footprints that allow the components to be installed in downhole tools.

Devices in accordance with the present disclosure may be configured for combined gas chromatography and mass spectroscopy optimized for relatively high pressure operation. Gas chromatographs use chromatographic columns to separate molecular species within a sample fluid and thereby to extract information about the sample fluid. A chromatographic column has a stationary phase fixed inside the column and a mobile phase which is a carrier gas, such as, helium that flows through the column. The sample is collected, injected into the column and then transported by the carrier gas into and through the column. If the sample is in a liquid state, the sample may first be injected into a vaporization chamber to be vaporized then transported through the column. As a sample progresses through the column, the individual molecular components are slowed down based on their affinity to the stationary phase. At the outlet of the column, a detector measures the quantity of each component as it exits the column. The calibrated retention time, i.e., the time a component spends in the column, identifies the component.

In one or more embodiments, devices may include a gas chromatograph may be used in combination with a detector such as a thermal conductivity detector (TCD). Standard GC-TCD configurations may have a detection limit of about 500 ppm, which may be limited in resolution and lack the ability to identify individual components of fluids and gases detected downhole. In some embodiments, a mass spectrometer may be used in combination with GC-TCD to identify additional fluid and gas components, and may increase measurement sensitivity and lower detection limits of the device. Lower detection limits for hydrogen sulfide, mercaptans, corrosion-inducing agents, and oxidants may increase worksite safety and enable an operator to make informed decisions about selection of wellbore casing and other tools depending on expected levels of oxidative materials present within a given wellbore.

Devices in accordance with the present disclosure may be configured as part of a downhole tool. While standard mass spectrometers may use turbo-molecular pumps to generate molecular flow conditions such as below 10⁻⁴ Torr, the pumps used to achieve these pressures are vulnerable to shock and vibration, and malfunctions of rotors and or bearings under high pressure, high temperature conditions, and corrosion in the presence of oxidants and other incompatible chemicals that may be present in wellbore fluids. However, devices in accordance with the present disclosure may be configured to be more robust against shock and vibration and to withstand higher operating temperatures than encountered in surface measurements, such as those present in a downhole environment. For example, operation at higher pressures above >10⁻³ Torr may enable mass spectrometers in accordance with the present disclosure to perform using scroll pumps and other components design to operate under harsh conditions.

In one or more embodiments, wellbore tools in accordance with the present disclosure may include a testing-while-drilling. With particular respect to FIG. 1, a testing-while-drilling device 100 may be provided into a wellbore, which may include a stabilizer with one or more blades 110 configured to engage a wall of the wellbore 110. The testing-while-drilling device 100 may be provided with a plurality of backup pistons 124 configured to assist in applying a force to push and/or move the testing-while-drilling device 100 against the wall of the wellbore 102. A probe assembly 114 may extend from the stabilizer blade 110 of the testing-while-drilling device 100. The probe assembly 114 may be configured to selectively seal off or isolate selected portions of the wall of the wellbore 102 to fluidly couple to an adjacent formation 117. Thus, the probe assembly 114 may be configured to fluidly couple components of the testing-while-drilling device 100, such as pumps 126 and/or 118, to the adjacent formation 117. Once the probe assembly 114 fluidly couples to the adjacent formation 117, various measurements may be conducted. For example, a pressure parameter may be measured by performing a pretest. Alternatively, or additionally, a sample may be withdrawn from the formation 117 via the probe assembly 114, and this sample may be analyzed using the ionization and spectrometry methods described above, possibly in conjunction with an ionization and/or spectrometry device also positioned within the device 100 and/or another component of the drill string.

The pump 118 may be used to draw subterranean formation fluid 108 from the formation 117 into the testing-while-drilling device 110 by the probe assembly 114. The fluid may thereafter be expelled through a port into the wellbore, or it may be sent to one or more fluid analyzers disposed in a sample analysis module 492, which may receive the formation fluid for subsequent analysis. Fluid analyzers may include one or more spectrometers and analyzers to interpret spectral data therefrom, such as to determine fluid composition utilizing the ionization and spectrometry methods in accordance with the present disclosure. The sample analysis module 106 may also be configured in some embodiments to perform such analysis on fluid obtained from the wellbore and/or drill string. For example, the sample analysis module 106 may be configured for use in mud-gas logging operations, wherein gas extracted from mud before and/or after the bit is analyzed to determine composition and/or concentrations; as described herein.

The stabilizer blade 110 of the testing-while-drilling device 100 may be provided with a plurality of sensors 112, 116 disposed adjacent to a port of the probe assembly 114. The sensors 112, 116 may be configured to determine petrophysical parameters such as saturation levels of a portion of the formation 117 proximate the probe assembly 114. For example, the sensors 112 and 116 may be configured to measure electric resistivity, dielectric constant, magnetic resonance relaxation time, nuclear radiation, and/or combinations thereof.

The testing-while-drilling device 100 may include a fluid sensing unit 122 through which the obtained fluid samples and/or injected fluids may flow, and which may be configured to measure properties of the flowing fluid. It should be appreciated that the fluid sensing unit 122 may include any combination of conventional and/or future-developed sensors within the scope of the present disclosure.

A downhole control system 104 may be configured to control the operations of the testing-while-drilling device 100. For example, the downhole control system 104 may be configured to control the extraction of fluid samples from the formation 117, wellbore and/or drill string, the analysis thereof, and any pumping thereof, for example, via the pumping rate of the pumps 126 and/or 118.

The downhole control system 104 may be configured to analyze and/or process data obtained from the downhole sensors and/or disposed in the fluid sensing unit 122 or from the sensors 112, and/or the fluid analysis module 106. The downhole control system 104 may be further configured to store measurement and/or processed data, and/or communicate measurement and/or processed data to another component and/or the surface for subsequent analysis.

While the testing-while drilling device 100 is depicted with one probe assembly, multiple probes may be provided with the testing-while drilling device 100 in accordance with the present disclosure. For example, probes of different inlet sizes, shapes (e.g., elongated inlets) or counts, seal shapes or counts, may be provided. Wellbore tools in accordance with the present disclosure may be designed to include the detection components on a logging sonde or drill string.

Turning to FIG. 2, an example well site system according to one or more aspects of the present disclosure is shown. The well site may be situated onshore (as shown) or offshore. A wireline tool 212 may be configured to measure a portion of a wall of a wellbore penetrating a subsurface formation 206. A wireline tool 212 may be suspended in the wellbore 208 from a lower end of a multi-conductor cable 202 that may be spooled on a winch at the surface. Cable 202 may be communicatively coupled to an electronics and processing system 204. The electronics and processing system 204 may include a controller having an interface configured to receive commands from a surface operator. In some cases, the electronics and processing system 204 may further include a processor configured to implement one or more aspects of the methods described herein.

The example wireline tool 212 may include a tool housing 208 protecting the internals, a central flow line 210 running through the body of the tool connecting the sample bottle 240 to other components such as fluid pump 238 and probe assembly 228. During operation, a sample 234 may be drawn into sample inlet and/or injection valve 236 and carried to the analytical module. The analytical module contains a gas source 214 in connection with a vaporization chamber 216 and chromatography column 220 in line with a thermal conductivity detector (TCD) 222. The mass spectrometer module contains the mass analyzer 224, which is pressure-regulated by vacuum pump 226.

Tools in accordance with the present disclosure may be arranged in various configurations between the gas chromatograph, detector, and mass spectrometer. With particular respect to FIG. 3, a flow diagram is shown indicating a possible configuration of a wellbore analysis tool in accordance with the present disclosure. To begin a downhole measurement, a sample is drawn from the wellbore using a sample acquisition system at 302 and, in some embodiments, passed through a filter 304 to remove solid debris and other materials. A gas emitted from a gas source 308 is then used to carry a sample introduced by the injection valve 310 into the vaporization chamber 312. The vaporized sample and carrier gas are then passed through the chromatography column 314 to separate the sample into various components.

Depending on the system configuration, the outlet of the gas chromatography column may send the sample to a thermal conductivity detector 316 for component analysis. The outlet of the thermal conductivity detector may be connected to the inlet of a mass spectrometer 318 in some embodiments, which may receive the sample components, along with gas from a source 306. In one or more embodiments, an ionizable gas such as nitrogen may be added from source 306 to increase sample ionization prior to introduction into the mass spectrometer module of the wellbore tools.

However, gas supplementation from 306 may be omitted in some embodiments in which sample volume and carrier gas permit MS measurement. In some embodiments, the thermal conductivity detector may be omitted and the sample may exit the chromatography column 314 and pass directly to the inlet of the mass spectrometer 318. Once the sample passes into the mass spectrometer from inlet 318, vacuum generated from a vacuum source 326 draws the sample through ionizer 320, into the mass analyzer 322, and to MS detector 324. Following measurement, the sample leaves the system and is discarded as waste gas 328. In one or more embodiments, one or both of detectors 316 and 324 may be monitored and/or controlled by a computer processor.

With particular respect to FIG. 4, a flow diagram is shown indicating another configuration of a wellbore analysis tool in accordance with the present disclosure. To begin a downhole measurement, a sample is drawn from the wellbore using a sample acquisition system at 402 and, in some embodiments, passed through a filter 404 to remove solid debris and other materials. A gas emitted from a gas source 408 is then used to carry a sample introduced by the injection valve 410 into the vaporization chamber 412. The vaporized sample and carrier gas are then passed through the chromatography column 414 to separate the sample into various components.

As the sample exits the chromatography column 414, the sample may be divided into two streams. A first stream may be directed to a thermal conductivity detector 430 and discarded as waste gas 432. The second stream may direct the sample to the inlet of a mass spectrometer 416. Once the sample passes into the mass spectrometer from inlet 416, vacuum generated from a vacuum source 426 may draw the sample through ionizer 420, into the mass analyzer 422, and to MS detector 424. Following measurement, the sample leaves the system and is discarded as waste gas 428. In one or more embodiments, one or both of detectors 430 and 424 may be monitored and/or controlled by a computer processor.

With particular respect to FIG. 5, an embodiment of a GC-MS in accordance with the present disclosure is shown. During operation, a flow line 502 initially contains the sample prior to passage into the GC by injection valve 504. The injection valve 504, as well as the other injection valves discussed herein, are rotary valves, although in some examples other types of valves may be provided. The sample is passaged with a carrier gas emitted by gas source 506 into vaporization chamber 508 and the vaporized sample is separated into various components in column 510, which may be heated to maintain vaporization using oven 512. Following passage through the GC module, the vaporized sample components are carried into the mass spectrometer component containing a mass analyzer 516 such as a cylindrical ion trap (CIT). Once the sample is in the mass spectrometer module, the sample is ionized by an ionization source 514 such as a glow discharge ionizer (GDI), further separated by the mass analyzer 516, and passaged to a detector 518 such as a Faraday cup. In some embodiments, the sample exiting the GC module may be combined with an ionizable gas from secondary gas source 524. The mass spectrometer may also maintain vacuum during operation using a vacuum pump 520 such as a scroll pump or other vacuum source. Following analysis, the sample components may pass into waste line 522 for appropriate disposal or recycling.

FIG. 5 also shows a schematic diagram of various electronic components adapted for use in connection with the exemplary fluid analysis sampling in accordance with embodiments of the present disclosure. According to at least one embodiment, a microprocessor 534 generally represents any form of computing or controlling device capable of performing any number of logic and/or controlling operations. In many embodiments, microprocessor 534 addresses and controls the operation of the valve 504, carrier gas source 506, temperature controller 532, radio frequency generator 526 and high voltage (HV) source 524. In some embodiments, microprocessor 534 may also be configured to receive telemetry data for a wellbore under analysis.

Although not specifically illustrated in FIG. 5, the output of reference detector 518 may be connected to one or more current amplifiers (I/V) 528, and/or an analog-to-digital (A/D) converter 530. A current amplifier 528 may convert the signal detected by detector 518 into a voltage, and/or an A/D converter 530 may convert the analog signal into a digital one. The resulting signal, which in many embodiments digitally represents the intensity of ion current detected by detector 518, may then be supplied to microprocessor 534 for use in computing the peak areas of the MS, FID or TCD spectrum of the vaporized fluid (gas) sample. Thus, in accordance with the signals supplied by the MS, TCD or FID, microprocessor 534 computes the presence and/or amount of any of a number of chemical compositions in vaporized fluid or gas sample.

Although the foregoing descriptions of FIG. 5 have been provided with reference to discrete elements and circuits, one of skill in the art having the benefit of this disclosure will recognize that one or more of these discrete circuits may be combined into a single integrated circuit or chip. For example, while transimpedance amplifier 528 and A/D converter 530 have been illustrated as discrete elements, the function of these two circuits may be combined into a single integrated circuit, resulting in increased savings in space and efficiency. The temperature and operation of the column 510 in oven 512 may be controlled by temperature controller 532, which may in turn be controlled by microprocessor 534.

With respect to FIG. 6.1, a first view of a quadrupole mass analyzer in accordance with embodiments of the present disclosure is shown. The interior of the mass analyzer contains an arrangement of four cylindrical electrodes with two electrodes 602 connected to negative polarity DC−RF voltage supply, and the remaining electrodes 604 connected to positive polarity DC+RF voltage. With particular respect to FIG. 6.2, a cross-section of the quadruple mass analyzer is shown during operation. A sample entering the mass analyzer is converted to ions by ionization source 606 and passaged into the channel created by positive electrodes 604 and negative electrodes 602, where the trajectory of the ions are modified, depending on molecular weight or conformation, for example, in a RF voltage-dependent fashion. Following separation by the arranged electrodes, the separated ions pass to detector 608. Representative ion trajectories are shown at 610.

With respect to FIG. 7, a quadrupole ion trap mass analyzer is shown. A sample entering the mass analyzer encounters an ionization source 702 and the resulting ions are passed into the field of ring electrode 704 having end caps 706. Once charged ions enter the mass analyzers, ions are circulated in the space within the center of the electrode, and the RF voltage supply 708 is modulated to selectively emit ions that are passed to detector 710 in a controlled fashion. A representative ion trajectory is shown at 715.

With respect to FIG. 8, an exploded view of a cylindrical ion trap (CIT) mass analyzer is shown in accordance with embodiments of the present disclosure. A sample entering the CIT passes the ionization source 802, end cap 804, and through a plurality of ring electrodes 806 and insulators 808 before reaching the detector 812. The CIT mass analyzer is controlled by an RF voltage supply 810 that may be modulated to resolve molecular species of varying weights and conformations.

In one or more embodiments mass spectrometers may operate under temperature ramp or constant temp operational modes. In some embodiments, variables such as vacuum strength or RF may be adjusted to optimize the outcome of each measurement. Furthermore, to expand the detection range, the sample concentration can be reduced by dilution or other methods. Adaptations can be done automatically as a gradual or a stepwise change.

In one or more embodiments, wellbore measurements may be obtained by adjusting pressure within the mass analyzer of the MS depending on the concentration of molecules that is measured. With particular respect to FIG. 9, pressure may be iteratively modified in order to increase the analytical output from the sample. In one or more embodiments, pressure may be set to an initial value such as 0.1 Torr at 902. The sample may then be measured at 904 to determine mass concentration. Pressure may then be increased at 906 and then mass concentration may be determined at 904 through a number of iterations represented by 908.

The MS receives the separated components from the GC in a predictable order, often in which components become heavier and in lower concentration as a function of time. However, method in accordance with the present disclosure may account for anomalies from this pattern such as the presence of aromatic or branching components that may travel differently that the linear alkane counterparts, and the presence of various contaminants from mud filtrates and other wellbore fluid additives. In one or more embodiments, algorithms may be developed in which the RF frequency of the mass analyzer is adjusted following one or more mass spectrum measurements to increase sensitivity and resolution of individual components in mixtures eluted from the GC. For example ion trap and quadrupole mass analyzers are operated by applying a combination of RF and DC voltages to the electrodes of the respective mass analyzer to create a quadrupole electric field. This electric field traps ions in a potential energy well at the center of the analyzer. The mass spectrum is then acquired by scanning the RF and DC fields to destabilize low mass to charge ions. Destabilized ions are ejected through a hole in one endcap electrode and strike a detector, which allows a mass spectrum to be generated by scanning the fields so that ions of increasing m/z value are ejected from the cell and detected.

With particular respect to FIG. 10, a workflow for iteratively adjusting the RF of a mass analyzer in order to analyze heavier components is shown. However, at different RF frequencies the fragmentation pattern might be different too. In some embodiments, two or more RF may be used intermittently during operation in order to determine if altering the RF presents a differing fragmentation pattern that enables additional compounds to be resolved. For example, during measurement, the MS may be operated at a RF frequency suitable for detecting low mass components at 1002. Following the initial measurement, the mass of the sample components is determined at 1004, and the RF frequency is lowered at 1006, and mass is again determined at 1004. The RF modulation and mass determination may be performed iteratively according to 1008 until the operator is satisfied that all components of the sample have been identified and/or the error has been lowered to an acceptable lever. Furthermore, other variables like vacuum strength can be adjusted to optimize the outcome of each measurement. Furthermore, to expand the detection range the sample concentration can be reduced by dilution or other methods. All these automatic adaptations can be done automatically as a gradual or a stepwise change.

In the following section, the individual components of wellbore measurement tools will be discussed in greater detail in the following sections.

Gas Chromatograph

Gas chromatographs (GC) in accordance with the present disclosure may be installed within a wellbore tool as discussed above with respect to FIGS. 1 and 2. GC devices may contain a gas source that generates and maintains an inlet pressure for the gas chromatograph between 750 to 4500 Torr in some embodiments. Carrier gases include inert gases such as helium, hydrogen provided from a compressed gas cylinder or charged metal hydrides. Carrier gas sources may include a fraction of an ionizable gas such as nitrogen that is included at a concentration of 0.1% to 10% by volume of the total carrier gas in some embodiments, and from 1% to 3% in some embodiments.

Gas Chromatograph Detectors

GC in accordance with the present disclosure may include a thermal conductivity detector to analyze gaseous and fluid components. TCD detectors may be limited to certain carrier gases such as helium or hydrogen and may be unable to differentiate some components in a sample. TCDs may also have a lower detection limit of about 500 ppm.

In one or more embodiments, systems in accordance with the present disclosure may operate under work under reduced pressure and downhole temperatures. Systems may contain a gas chromatograph, a TCD, and a high pressure (>10⁻³ bar) mass spectrometer. In some embodiments, systems may be designed to fit within a tool that may be emplaced within a wellbore, including as part of a tool string.

In one or more embodiments, the inlet of the TCD may be connected to the output of the GC column. In some embodiments, the inlet of the MS may be connected to the outlet of the TCD or directly from the GC. MS in accordance with the present disclosure may contain an ionizer, a mass analyzer, and an ion detector. The mass analyzer of the MS may be an ion trap analyzer in some embodiments, or a quadrupole mass analyzer in other embodiments. Connections between the individual components may be gas- or fluid-tight seals suitable for the application.

Mass Spectrometer

In one or more embodiments, devices in accordance with the present disclosure may include high pressure mass spectrometers such as quadrupole and ion trap mass spectrometers. MS in accordance with the present disclosure often contain several components, including an inlet, an ion source, a mass analyzer, and an ion detector. In some embodiment, MS may include a controller to activate the detector, one or more pumps, and a vacuum system to maintain pressure levels. Vacuum systems may include scroll pumps, a hydrogen generator such as metal hydride or a combination of both.

In one or more embodiments, the vacuum system may generate a pressure in an MS between the 0.001 Torr and 10 Torr and capable of handling an inlet pressure for the mass spec which is below 600 Torr. In some embodiments, a flow restrictor maybe placed between the outlet of the TCD and the mass spectrometer to maintain pressure at the TCD. MS in accordance with the present disclosure may include a second gas source with an ionizable gas such as nitrogen that is added just before the mass spectrometer. For example, after the TCD if the MS is connected to the outlet of TCD or after the column if the mass spectrometer is directly connected to the outlet of the column. MS in accordance with the present disclosure may operate at in a pressure regime that ranges from 10⁻³ to 10 Torr in some embodiments, and from 10⁻² to 10 Torr in other embodiments.

Ion Sources

MS in accordance with the present disclosure may include an ionizer that ionizes the incoming analyte from the GC. Ionizers may include a soft ionizers that remove a single electron from molecules within the analyte and attempt to minimize molecule fragmentation, creating what is often referred to as a singly-charged molecular ion. In one or more embodiments, additional gas that can easily be ionized may be added to the analyte prior to passage to the ionizer to increase the degree of sample ionization. In some embodiments, nitrogen may be used to induce chemical ionization of the analyte.

Soft ionization techniques such as glow discharge ionization, electrospray ionization, photionization, electron ionization, and chemical ionization, may be used in devices in accordance with the present disclosure to produce ions from hydrocarbons and other analytes, and are discussed in further detail below.

A glow discharge ionization source includes a discharge chamber having an entrance orifice for receiving the analyte particle beam or analyte vapors, and a target electrode and discharge electrode therein. An electric field applied between the target electrode and discharge electrode generates an analyte ion stream from the analyte vapor, which is directed out of the discharge chamber through an exit orifice and into a mass analyzer.

In electro spray ionization, a sample solution enters an electrospray chamber through a hollow needle which is maintained at a few kilovolts relative to the walls of the electrospray chamber. The electrical field charges the surface of the liquid emerging from the needle, dispersing it by coulomb forces into a spray of fine, charged droplets. At this point the droplets become unstable and break into daughter droplets. This process is repeated as solvent continues to evaporate from each daughter droplet. Eventually, the droplets become small enough for the surface charge density to desorb ions from the droplets into the ambient gas. These ions, which include cations or anions attached to solvent or solute species which are not themselves ions, are suitable for analysis by a mass spectrometer.

Photon Ionization is another ionization technique in which analytes absorb light (typically a single photon in the vacuum ultraviolet range), and that photon energy is used to eject an electron. If the photon energy is just above the ionization potential, little energy will be leftover for fragmentation, providing soft ionization.

In electron ionization, an electron beam is directed at the analyte-containing sample. Some of the translational energy of the electrons is used to ionize the analytes. Typically 70 eV electrons are used, but that energy is much greater than typical ionization potentials (around 10 eV), and that excess energy typically leads to extensive fragmentation. Using low electron energy (around 15 eV) produces fewer fragments with less ionization efficiency.

In chemical ionization various gases are first ionized (using electron ionization for example), and those ionized gases are allowed to react with an analyte. Interaction with ionized gases may impart an electrical charge to the analyte, which is then passed into the mass analyzer. The efficiency of this process may vary greatly for different analytes, providing a contrast mechanism in some cases. On the other hand, chemical ionization techniques may result in the formation of complexes between the analyte and the ionization gas, which can obscure analysis results.

Mass Analyzers

Mass spectrometers in accordance with the present disclosure may include mass analyzers such as ion traps, linear and ion trap quadrupole, and Loeb-Eiber filters.

Quadrupole mass spectrometers (QMS) are designed from four cylindrical rods electrically connected to RF and DC voltage sources as discussed above with respect to FIGS. 6.1 and 6.2. The RF to DC ratio allows selective transmission of ions of a particular m/z value to travel in a stable trajectory along the z-axis. A mass spectrum is obtained by ramping the amplitude of the RF and DC voltages to sweeps ions of increasing m/z toward the detector.

A quadrupole ion trap (QIT) mass analyzer operates according to similar principles as a QMS, but may allow ions of multiple m/z values to be trapped simultaneously in a region of stability defined by solutions of the Mathieu equations described by, in some embodiments, the parameters q_(z)=4 zV/mr²ω² and a_(z)=−8 zU/mr²ω² where z is the electric charge, V the amplitude of the RF voltage, U is the amplited of the DC voltage, m is the mass of the ion, r is the radius of the ion trap, and co is the angular frequency of the RF potential. QIT mass analyzers in accordance with the present disclosure may eject trapped ions oscillating at frequencies proportional to the fundamental frequency ω when operating in mass selective instability mode, in sequence from low to high m/z values along the q_(z) axis, with the DC potential held at zero, by ramping the amplitude of the RF voltage as q_(z) approaches 0.908 whereupon they are ejected, as discussed above with respect to FIG. 7.

Cylindrical ion trap (CIT) mass analyzers may be function similarly to the QIT, with the exception that hyperbolic electrodes of the QIT are replaced by a flat ring electrode. In some embodiments, miniaturized CIT mass analyzers may compensate for the loss of trapping capacity resulting from the smaller trap radius by including an array of traps with identical radii, as discussed above with respect to FIG. 8 and in the examples below.

Mass analyzers may also include Loeb-Eiber filter such as those described in U.S. Pat. No. 7,772,546. Loeb-Eiber filters may be suited for operation at relatively high pressures. In one or more embodiments, the collisional dampening of ions up to the mass filter thermalizes the kinetic energy of the ions which makes the filtering more effective. In some embodiments, Loeb-Eiber filters may be fabricated using traditional manufacturing techniques or MEMS technology.

Detectors

Mass spectrometers in accordance with the present disclosure may incorporate one or more detectors that measure ionized analyte components. Detectors may measure ions based upon their charge or momentum. In one or more embodiments, detectors may include a Faraday cup that measures ion current traveling through the mass analyzers of the mass spectrometer. Other detectors may include electron multipliers, channeltrons and multichannel plates.

Applications

GC-MS tools in accordance with the present disclosure may be operated in a number of modes depending on the application. In one or more embodiments, data output may be formatted as total ion current (TIC) chromatographs representing the summed intensity across the entire range of masses being detected at during every measurement collected during the analysis. In some embodiments, data output may take the form of a selected-ion monitoring (SIM) chromatogram representing a single m/z value or subrange of values measured over the duration of sample analysis.

Low Concentration Analyte Detection

Methods in accordance with the present disclosure may increase the sensitivity of a mass spectrometer operating in TIC mode or SIM mode. In one or more embodiments, GC-MS in accordance with the present disclosure may possess detection limits in the range of single digit ppm. In some embodiments, a wellbore tool incorporating a GC-MS in accordance with the present disclosure may be used to detect sample concentrations at a concentration in the range of 1 ppm or greater.

GC-MS tools in accordance with the present disclosure may be used to determine analyte concentration by generating a chromatogram that is then used in combination with a calibration curve obtained from a reference analyte of known concentration. For example, a series of calibration samples may be measured using a GC-MS operating under similar conditions expected downhole, and the peak areas from the resulting chromatographs may be used to determine the concentration of the respective analyte in an unknown sample.

In one or more embodiments, GC-MS in accordance with the present disclosure may be employed for the detection of sulfur components within a wellsite operating environment. The concentration of sulfur components, such as hydrogen sulfide, as low as 5 ppm may be harmful to operators and installed equipment. In some embodiments, determination of the concentration of sulfur components may be monitored to ensure the proper level of corrosion resistance is maintained when selecting completions and uphole equipment. Methods in accordance with the present disclosure directed to monitoring the presence of sulfur components may include the use of selected-ion monitoring (SIM) in the range of 32-34 m/z to identify and quantify the various components. Concentration of sulfur components may be determined, for example, by establishing a calibration curve for a selected analyte as discussed above.

GC Peak Deconvolution

In one or more embodiments, methods in accordance with the present disclosure may be used to deconvolve overlapping peaks output in a GC chromatogram. During measurement, components having similar mass or molecular shape may elute from the GC at the same time as other components, which may appear in a chromatogram as a single peak. However, methods in accordance with the present disclosure may be used to resolve the components on the basis of mass, chemical structure, fragmentation or addition patterns using mass spectroscopy.

Chromatogram deconvolution methods in accordance with the present disclosure may include measuring a sample and obtaining a gas chromatogram output. The eluted fraction corresponding to the combined sample peaks is then analyzed using a mass spectrometer, which outputs the molecular weights of the co-eluting components. In some embodiments, the ratio of the peak intensity of the components may be used for rapid detection using GC-MS to determine the ratio between two or more components that elute at the same time from a chromatograph. For example, the relative signal intensities of the components in the output of the mass spectrometer may then be used as an indicator of the relative contribution of each component to the peak observed in the gas chromatogram.

In one or more embodiments, the ratio of two components obtained from the output of the mass spectrometer may be used in conjunction with the output of a TCD to establish concentrations for each of the components. For example, in a case where two components are distinguishable by MS chromatogram, but register as a single peak on a TCD chromatogram, the ratio of the two components may be used to allocate the concentration between the two components. In practice, the components are also identified, such as by matching of the fragmentation patterns to an existing library of identified components by MS, and the known molar mass of the components are used to derive a concentration. Similarly, in the case in which a peak is too small to be determined by the TCD, but is proximate to a peak detectable by the TCD, the ratio of these two peaks can then be used to estimate a concentration for the component in the smaller peak by relating it to the TCD measurement.

In some embodiments, the determination of concentration from a ratio of two components identified by MS may be performed by determining relative concentration between two components of the sample based on the output of the mass spectrometer, identifying the two components by matching the output of the mass spectrometer to a library of known components, determining a combined concentration of the two components of the sample based on the output of a thermal conductivity detector configured to receive an output from the gas chromatograph, and determining a concentration for the two components using the identity of the two components, the relative concentration of the two components, and the combined concentration of the sample based on the output of a thermal conductivity detector.

In one or more embodiments, methods in accordance with the present disclosure may be adapted for group analysis of multiple components. In some embodiments, group analysis may utilize SIM to separate and analyze complex grouping of components. For example, aromatic species may all exhibit a GC peak representative of the benzene ring at 78 m/z or in combination with nitrogen addition at 106 m/z. The analysis of components within this range may then be separated on the basis of molecular weight, selective ionization, and fragmentation patterns using a mass spectrometer in accordance with the present disclosure. Group analysis may also be applied to other component mixtures such as polyaromatics, heteroatomic rings containing sulfur and oxygen, and the like.

In one or more embodiments, the ionization method may be tuned to selectively ionize a particular type of analyte. For example, N-alkanes will have a distinct peak in the TCD spectrum, whereas their visibility in a total ion count chromatogram will be suppressed due to the inefficient ionization process of the n-alkanes. In contrast, the branched alkanes often show up as broad overlapping peaks in the TCD results, but can give a stronger more defined peak in the total ion count chromatogram. In one or more embodiments, selection of the ionization technique may be used in combination with a TCD to identify the branched alkane and n-alkane components.

The ratio of specific components in a hydrocarbon stream may also be used in some embodiments to detect connectivity between zones, such as where the ratio of the components is characteristic to one or more respective zones. For example, if an oilfield a single zone, then the composition of the oil is expected to be in equilibrium and the ratios between components with similar molar mass should be relatively homogeneous as a function of depth and within neighboring wells in the field. However, variations in the molar mass ratios between two sampling points may signify that the fluids are not in equilibrium, which may also indicate the presence of barriers between zones. By way of example, Halpern C7 correlations may be used to differentiate samples through differences in the ratios between the five substituted pentanes with a total of seven carbon atoms, i.e. 2,2-dimethyl pentane, 2,3-dimethyl pentane, 2,4-dimethyl pentane, 3,3-dimethyl pentane, and 3-ethyl pentane.

Biodegradation Characterization

Methods in accordance may be used to quantify the level of biodegradation in a hydrocarbon sample, and enable the selection of pseudocomponents in cases in which the GC chromatogram is ambiguous or poorly defined. The selection of pseudocomponents in hydrocarbon mixtures and other non-biodegraded oils may have characteristic peaks that allow grouping of the various components into pseudocomponents having similar boiling points and carbon number, but slight variation in molecular weight, branching, functionalization, and the like. In GC analysis, pseudocomponents are defined as the all components eluting after n−Cn to, and including, n−C(n+1).

However, alkanes and other organics may undergo biodegradation by various microorganisms within a reservoir, decreasing the number of n-alkanes and generating a number of byproducts. As an example, a representative oil sample with little or no biodegradation as evidenced by the distinguishable carbon number peaks is shown in FIG. 11. By comparison, a biodegraded oil sample is shown in FIG. 12 in which degradation products obscure the carbon number peaks and render peak identification more difficult. Biodegradation can interfere with the ability to identify pseudocomponents, particularly as the n-alkanes used as distinct chromatographic landmarks for the grouping of pseudocomponents are the first to be reduced in concentration by biodegradation. In one or more embodiments, MS chromatograms may be used to identify elution times and other landmarks that can be used to define pseudocomponent boundaries.

Library Matching with Background Subtraction

In one or more embodiments, methods may include the analysis of complex component mixtures using comparison of GC-MS output to compiled library data for the expected chemical components in the sample. In some embodiments, use of library matching may enable the quantification of the co-eluting components. Library matching methods may distinguish components having the same mass on the basis of varied fragmentation in some embodiments. Further, library matching methods may allow the subtraction of molecular weights and fragmentation patterns of known components from a chromatogram output, which may enable an operator to isolate and identify novel and unknown components in a sample.

Applications of library matching in accordance with the present disclosure may include comparing the measured response from a GC-MS to a library including known chemical components to aid in identification of known analytes in a sample, including the quantification of molecular weight and concentration of individual analytes. Methods in accordance with the present disclosure that utilize library matching may include the establishment of a library of chemical components from existing and projected GC-MS chromatograms. However, while described as a starting point, a chemical library may be assembled at any stage in the analysis, including after the initial sample measurement downhole.

EXAMPLES

In the following examples, an analyte is measured using a high-pressure gas chromatograph/mass spectrometer combination tool and MS is used to increase the accuracy of component identification and deconvolve multiple overlapping peaks in some instances.

A sample taken from the headspace of a dead oil sample containing hydrocarbon mixtures of components C1 to C8 and measured using a GC-MS in accordance with the present disclosure. The GC component of the device utilized an alumina BOND/Na₂SO₄ column and is using helium as a carrier gas. The MS component was equipped with a glow discharge ionizer and a miniature ion trap mass analyzer, and a faraday cup detector. During operation, the GC column was cycled at 60° C. for 2 minutes, then heated to 200° C. at 10° C./min for 10 minutes. The MS ion trap was operated at a starting RF of 6.97 MHz and an internal operating pressure of 3 Torr. The MS measurements were done with a frequency of 2 measurements per second with every measurement averaging 15 mass scans at each of the three RF frequencies.

With particular respect to FIG. 13, a diagram for the total ion count (TIC) for the sample is shown at a frequency of 6.97 MHz. With particular respect to FIG. 14, the specific ion measurement at 58 m/z is shown for the same sample. FIG. 15 also shows the sample measured in FIG. 14 with the total ion count according to a logarithmic scale. With particular respect to FIG. 16, the GC fraction at 655-660 seconds, which correlates to C6 hydrocarbons, is analyzed with MS at 58 m/z, 70 m/z, and 86 m/z. The results demonstrate that it is possible to deconvolve the co-eluting fractions between 655 and 660 seconds from the GC. Furthermore, the spectrum demonstrates that it is possible to distinguish n−C6 at 680 seconds from the other C6 isomers by observing the particular fragmentation pattern.

In the next example, combined GC-MS is used to resolve the peaks for the same sample. The specific ion measurement is shown for the C7 fraction from the GC at 58 m/z, 72 m/z, 86 m/z, and 100 m/z are shown in FIG. 17. With particular respect to FIGS. 18-20, the mass spectrum of three C7 components eluting at 786, 792, and 797 seconds, respectively, are shown to demonstrate the ability of a GC-MS to resolve species that would overlap if a column or temperature regime is used with less resolving power than the current measurement. For example, overlap in spectra may be expected in cases in which downhole conditions involve high ambient temperatures and cooling is more difficult.

In accordance with some examples, applicant has discovered that by providing and combining certain features, including a rotary valve and an ion trap or quadrupole mass analyzer, it is possible to operate a mass spectrometer at high pressures (greater than 10⁻² Torr). This in turn allows for more robust pumps (e.g., scroll pumps, screw pumps, piston pumps) which are—in contrast to typical mass spectrometry pumps—suitable for use in downhole conditions in a wellbore. It is further noted in this regard that the ion trap and quadrupole mass analyzers are scalable to small sizes that reduce the increased molecular collisions that occur due to higher pressures.

Although the preceding description has been described herein with reference to particular means, materials and embodiments, it is not intended to be limited to the particulars disclosed herein; rather, it extends to all functionally equivalent structures, methods and uses, such as are within the scope of the appended claims. In the claims, means-plus-function clauses are intended to cover the structures described herein as performing the recited function and not only structural equivalents, but also equivalent structures. Thus, although a nail and a screw may not be structural equivalents in that a nail employs a cylindrical surface to secure wooden parts together, whereas a screw employs a helical surface, in the environment of fastening wooden parts, a nail and a screw may be equivalent structures. It is the express intention of the applicant not to invoke 35 U.S.C. § 112(f) for any limitations of any of the claims herein, except for those in which the claim expressly uses the words ‘means for’ together with an associated function.

To the extent used in this description and in the claims, a recitation in the general form of “at least one of [a] and [b]” should be construed as disjunctive. For example, a recitation of “at least one of [a], [b], and [c]” would include [a] alone, [b] alone, [c] alone, or any combination of [a], [b], and [c]. 

The invention claimed is:
 1. A method comprising: emplacing a wellbore tool in a wellbore, the wellbore tool containing a gas chromatograph, a rotary valve configured to inject a fluid sample into the gas chromatograph, a mass spectrometer and at least one of a scroll pump, screw pump, or piston pump, wherein the mass spectrometer is configured to operate at a pressure greater than 10⁻² Torr, wherein an inlet for the mass spectrometer receives an output from an outlet of the gas chromatograph, and wherein the mass spectrometer comprises at least one of (a) an ion trap analyzer and (b) a quadrupole mass analyzer; measuring a sample from the wellbore using the wellbore tool; maintaining vacuum during at least a portion of operation of the mass spectrometer using at least one of the scroll pump, screw pump, or piston pump; determining a molecular weight of one or more components of the sample from the measured response of the wellbore tool; determining a relative concentration between two components of the sample based on the output of the mass spectrometer; identifying the two components by matching the output of the mass spectrometer to a library of known components wherein identifying is based upon, at least in part, matching one or more fragmentation patterns to the library; determining a combined concentration of the two components of the sample based on the output of a thermal conductivity detector configured to receive an output from the gas chromatograph; and determining a concentration for the two components using the identity of the two components, the relative concentration of the two components, and the combined concentration of the sample based on the output of the thermal conductivity detector.
 2. The method of claim 1, further comprising determining a concentration for the one or more components of the sample by comparing the measured response of the wellbore tool with a calibration curve established for the one or more components.
 3. The method of claim 1, wherein measuring a sample from the wellbore tool comprises separating the sample into one or more eluted fractions using the gas chromatograph, and wherein the method further comprises deconvolving the one or more eluted fractions into one or more deconvolved chromatograph peaks using the molecular weights determined for the one or more components of the sample corresponding to the one or more eluted fractions.
 4. The method of claim 3, wherein the ratio of the integrated area for deconvolved chromatograph peaks is used to determine the relative concentration of the one or more components of the fluid.
 5. The method of claim 3, wherein the one or more deconvolved chromatograph peaks comprise aromatics.
 6. The method of claim 1, wherein the mass spectrometer comprises a soft ionization source, and wherein the method further comprises deconvolving branched alkanes, cycloalkanes, and n-alkanes eluted from a gas chromatograph by selectively ionizing the branched alkanes with the soft ionization source and determining the molecular weights for the branched alkanes.
 7. The method of claim 1, further comprising separating one or more components of the sample into one or more pseudocomponents.
 8. The method of claim 1, wherein the mass spectrometer is configured to detect a sample component at a concentration in the range of 1 ppm or greater.
 9. The method of claim 1, wherein the mass spectrometer is configured to monitor a mass window in the range of 32-34 m/z and to output a selected-ion monitoring chromatogram.
 10. The method of claim 1, wherein the mass spectrometer is configured to detect one or more sulfur components.
 11. The method of claim 1, wherein the mass spectrometer comprises an ion trap mass analyzer.
 12. The method of claim 1, wherein the mass spectrometer comprises a quadrupole mass analyzer.
 13. A method comprising: establishing a library of one or more chemical components; emplacing a wellbore tool in a wellbore, the wellbore tool containing a gas chromatograph, a rotary valve configured to inject a sample into the chromatograph, a mass spectrometer and at least one of a scroll pump, screw pump, or piston pump, wherein the mass spectrometer is configured to operate at a pressure greater than 10⁻² Torr and wherein the mass spectrometer comprises at least one of (a) an ion trap analyzer and (b) a quadrupole mass analyzer; measuring a sample from the wellbore using the wellbore tool, wherein measuring a sample from the wellbore tool comprises separating the sample into one or more eluted fractions using the gas chromatograph; maintaining vacuum during at least a portion of operation of the mass spectrometer using at least one of the scroll pump, screw pump, or piston pump; comparing the measured response from the wellbore tool for the sample with results from the library of one or more chemical components; and determining a molecular weight of one or more components of the sample, wherein the method further comprises deconvolving the one or more eluted fractions into one or more deconvolved chromatograph peaks using the molecular weights determined for the one or more components of the sample corresponding to the one or more eluted fractions.
 14. The method of claim 13, further comprising determining a concentration for the one or more components of the sample by comparing the measured response of the wellbore tool for the sample with a calibration curve established for the one or more components.
 15. The method of claim 13, wherein the mass spectrometer is configured to detect a sample component at a concentration in the range of 1 ppm or greater.
 16. The method of claim 13, further comprising determining the concentration the one or more components of the fluid by comparing the measured response from the wellbore tool with a calibration curve established for the one or more components.
 17. The method of claim 13, wherein the mass spectrometer comprises a soft ionization source, and wherein the method further comprises deconvolving branched alkanes, cycloalkanes, and n-alkanes eluted from a gas chromatograph by selectively ionizing the branched alkanes with the soft ionization source and determining the molecular weights for the branched alkanes.
 18. The method of claim 13, wherein the mass spectrometer comprises an ion trap mass analyzer.
 19. The method of claim 13, wherein the mass spectrometer comprises a quadrupole mass analyzer.
 20. The method of claim 13, wherein the mass spectrometer is configured to detect one or more sulfur components.
 21. The method of claim 13, wherein the one or more deconvolved chromatograph peaks comprise aromatics. 